Fundamentals of Structural Chemistry

The following sections are included:

• PREFACE

• CONTENTS

The following sections are included:

• The characteristic motion of microscopic particles
  • Black body radiation and energy quantization
  • Photoelectric effect and photons
  • The wave-particle duality of microscopic particles of matter
  • The uncertainty principle

• The basic assumptions in quantum mechanics
  • Wavefunction and the states of microscopic particles
  • Mechanical quantities and operators
  • Eigenstate, eigenvalue and the Schrödinger equation
  • Superposition principle
  • Pauli's principle

• Schrödinger equation and its solution for particle in a one-dimensional box

• Problems 1

The following sections are included:

• The schrödinger equation and its solution for a single-electron atom
  • The Schrödinger equation for a single-electron atom
  • The method of separation of variables
  • The solution of the Φ-equation
  • Wavefunction of a one-electron atom

• The physical significance of quantum numbers

• The diagrams of wavefunction and electron cloud
  • The ψ-r and ψ²-r plots
  • The radial distribution diagram
  • Atomic orbital contours

• The structure of a multielectron atom
  • The Schrödinger equation and its approximation solution for a multielectron atom
  • The atomic orbital energy and binding energy of an electron
  • The building up principle for the ground-state atom

• Atomic spectra
  • The electronic state and the energy state of an atom
  • The spectrum of a one-electron atom
  • Spectrum of a multielectron atom
  • The applications of atomic spectra

• Periodic properties of elements
  • The ionization energy of an atom
  • The electron affinity of an atom
  • The electronegativity of an atom
  • The periodicity of elements and the periodic table

• Problems 2

The following sections are included:

• The structure of H₂⁺ and the nature of a covalent bond
  • The Schrödinger equation of H₂⁺
  • Solution of Schrödinger equation by using the variation method
  • The significance of integrals H_aa, H_ab, S_ab and the structure of H₂⁺
  • The nature of a covalent bond

• Molecular orbital theory and the structure of a diatomic molecules
  • The simple molecular orbital (MO) theory
  • The characteristic distribution and classification of molecular orbital
  • The structure of homonuclear diatomic molecules
  • The structure of heteronuclear diatomic molecules

• The structure of H₂ molecules and the valence bond theory
  • The valence-bond (VB) method for the solution of the structure of H₂
  • Valence bond theory
  • Comparison between the VB and the MO theories

• Molecular spectroscopy
  • Introduction
  • Rotational spectra of diatomics
  • The vibrational spectra of diatomics
  • Raman spectrum
  • The electronic spectrum of molecule

• Photoelectron spectroscopy
  • Theory
  • Photoelectron spectrum of diatomics

• Problems 3

The following sections are included:

• Symmetry operation and symmetry element
  • Rotational axes and operations
  • Centres of symmetry and the inversion operations
  • Planes of symmetry and the reflection operations
  • Rotatory-inversion axes and operations
  • Rotatory-reflection axes and operations

• Symmetry operations of a group and combination of symmetry elements
  • Definition of a group
  • Multiplication table of a group
  • Combination of symmetry elements

• Point groups of molecules
  • Classification of point groups of molecules
  • The differentiation of point groups of molecules

• The symmetry and optical activity of molecules

• The dipole moment and polarizability of molecules
  • Dipole moment and structure of molecules
  • The induced dipole moment and polarizability of molecules

• Representations of groups
  • Matrix representations of symmetry operations
  • The properties of character and the character table
  • Example on the applications of the character table

• Problems 4

The following sections are included:

• Valence shell electron pair repulsion theory (VSEPR)

• The theory of hybrid orbitals

• Delocalized molecular orbital theory

• HMO and the structure of conjugated molecule
  • HMO Theory
  • The HMO treatment of butadiene
  • The HMO treatment of cyclic conjugated polyene (C_nH_n)
  • Delocalized π bonds and the properties of molecules

• Symmetry of molecular orbitals and reaction mechanism
  • Some principles and concepts related to chemical reactions
  • Frontier-orbital theory
  • The Woodward-Hoffmann rules

• The bond lengths of bond energies of covalent bonds
  • The covalent bond length and the atomic covalent radii
  • The bond energy for a covalent bond

• Intermolecular interaction and the sizes and shapes of molecules
  • The interacting forces between molecules
  • Van der Waals' attraction and van der Waals' radii
  • The sizes and shapes of molecules

• Nuclear magnetic resonance spectroscopy
  • Nuclear magnetic moment and the principles of nuclear magnetic resonance
  • Chemical shifts
  • Nuclear spin-spin coupling

• Problems 5

The following sections are included:

• Introduction
  • Ligands
  • The development of theories on structure of complexes

• Ligand field theory
  • The molecular orbital of an octahedral ML₆ complex
  • The octahedral ligand field splitting energy Δ_o
  • Ligand field stabilization energy and the properties of complexes
  • The thermodynamic stability of complexes
  • Ligand fields of other polyhedra

• The structure and properties of complexes containing π bonds
  • Metal carbonyl complexes and small molecule complexes
  • Complexes of unsaturated hydrocarbons of π-complexes
  • Transition metal complexes of cyclopolyenes
  • The rules of isolobal analogy
  • Valency of atoms in complexes
  • Catalytic effect of ligands

• The structures and properties of transition metal clusters
  • Cluster geometries
  • Multiple M-M bonds in clusters
  • The catalytic nature of cluster compounds

• Problems 6

The following sections are included:

• Periodicity and lattices of crystal structures
  • The characteristics of crystal structure
  • Lattice and structural motif
  • Unit of lattices
  • Crystal defects

• Symmetry in crystal structures
  • Symmetry elements and symmetry operations
  • Unit cell
  • Crystal systems
  • Types of space lattice in crystals
  • Point group in crystallography
  • Space group
  • Indices of lattice point, line lattice and plane lattice

• The description and application of crystal structure

• X-ray diffraction of crystal
  • The source and property of X-rays
  • The direction of the diffracted ray
  • Intensity of the diffracted beam
  • Single crystal diffractometry
  • Polycrystalline diffractometry

• Problems 7

The following sections are included:

• The metallic bond and the general properties of metals
  • The ‘free-electron” model of the metallic bond
  • The band theory of solids

• Close packing of spheres and the structure of pure metals
  • Packing of identical spheres
  • A structural survey of pure metals
  • Atomic radii of metals

• The structures and properties of alloys
  • The structure of metallic solid solutions
  • The structure of metallic compounds
  • The structure of interstitial metallic compounds

• The structure of surface of metals

• Problems 8

The following sections are included:

• Some simple ionic crystal structures

• Ionic bond and lattice energy
  • The calculation and determination of lattice energy
  • The applications of lattice energy
  • The principles of variation of bond types

• Ionic radii
  • The determination of ionic radii
  • Effective ionic radii
  • The trend of variation of ionic radii

• The ionic coordination polyhedra and the linkage rules
  • The ionic radii ratio and the coordination polyhedra of ions
  • The linkages of coordination polyhedra
  • The Pauling rule of ionic crystal structure
  • The bond-valence method

• Structural chemistry of silicates
  • Introduction
  • The structure of SiO₂
  • The structural characteristics of silicates
  • Zeolite molecular sieve

• Problems 9

The following sections are included:

• Structural characteristics of non-metals
  • The structural characteristics of homonuclear non-metals
  • The structural characteristics of non-metallic compounds

• The structures of boranes and its related compounds
  • Diboranes
  • Metal alkyls

• Structural chemistry of hydrogen and the hydrogen bond
  • The natural existence of hydrogen
  • The hydrogen bond
  • The structural chemistry of water

• Problems 10

The following sections are included:

• Appendix 1 Exercises
  • Exercise 1. To construct the spatial distribution diagram of atomic orbitals
  • Exercise 2 To construct the energy curve of
  • Exercise 3 The three dimensional geometries and properties of molecules
  • Exercise 4 The HMO treatment of benzene
  • Exercise 5 Lattice and unit cell
  • Exercise 6 Polycrystalline X-ray diffraction method
  • Exercise 7 Packing of equal spheres
  • Exercise 8 Ionic crystal structure

• Appendix 2 Units, physical constant and conversion factors
  • Some international fundamental units
  • Some important derived units
  • Some common physical constants
  • Conversion between energy and other units of physical measurements
  • Atomic units (au)
  • Prefixes

• Appendix 3 Answers to Problems
  • Problems 1
  • Problems 2
  • Problems 3
  • Problems 4
  • Problems 5
  • Problems 6
  • Problems 7
  • Problems 8
  • Problems 9

• INDEX

• ERRATA